US5494964A - Polyesters based on hydroxyl-containing prepolymers of olefinically unsaturated monomers and their use as binders for electrophotographic toners - Google Patents

Polyesters based on hydroxyl-containing prepolymers of olefinically unsaturated monomers and their use as binders for electrophotographic toners Download PDF

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US5494964A
US5494964A US08/307,790 US30779094A US5494964A US 5494964 A US5494964 A US 5494964A US 30779094 A US30779094 A US 30779094A US 5494964 A US5494964 A US 5494964A
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weight
mixture
alkyl
polyester resin
hydroxyl
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Georg Meichsner
Thomas Wuensch
Rainer Dyllick-Brenzinger
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08786—Graft polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5272—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08755—Polyesters

Definitions

  • the present invention relates to novel polyester resins based on hydroxyl-containing prepolymers of olefinically unsaturated monomers and their use as binders for electrophotographic toners.
  • the present invention furthermore relates to electrophotographic toners containing these polyester resins as binders.
  • Electrophotographic toners have to meet a large number of requirements which arise from the copying process, toner production or the handling of the toners. Many of the requirements which a toner has to meet are determined by the binder, ie. by the toner resin.
  • a toner resin must be capable, for example, of readily dispersing additives such as carbon black, ferrites, magnetite, Aerosil, charge stabilizers and waxes. Homogeneous dispersing is necessary since otherwise toner particles having very different electrostatic properties may be present.
  • toner resin Another requirement is good millability of the toner resin.
  • reverse-jet mills are generally used. Some resins give toners which require very long times before they can be brought to the desired particle size, preferably from 5 to 15 ⁇ m, in a reverse-jet mill.
  • Another frequent problem in milling in the reverse-jet mill is the production of fine dust, ie. of particles which have a particle size which is less than 5 ⁇ m.
  • the shelf life of a toner is also influenced by the toner resin.
  • a resin which becomes soft at room temperature or at the temperatures prevailing in the copier and can stick together gives toner powders which can cake and are no longer free-flowing. Caking of the toner powder may also occur if a moisture-sensitive resin which is even only slightly hygroscopic is used.
  • resins which absorb moisture from the surrounding air lead to toners whose electrostatic properties are greatly dependent on the atmospheric humidity. The consequences are the occurrence of background and irregular blackening in solid areas on the copy.
  • a further problem is the increase in the fixing rate of an image transferred to the print medium (acceptor) by heat, ie. the increase in the cycle time of the copier.
  • the properties of a toner during fixing are greatly influenced by the melting behavior of the toner resin.
  • a higher fixing rate is achieved by using a resin having a low softening point.
  • this may result in the problem of hot offset, ie. some of the molten toner remains adhering to the hot fixing roller of the copier and is transferred to subsequent copies.
  • Polyesters having a lower softening point but poorer anti-offset properties are described in U.S. Aapplication No. 4,980,448 (2). These polyesters are obtainable by reacting a dicarboxylic acid component, a diol component and a crosslinking agent. However, in the preparation of these resins there is a danger that excessive crosslinking may occur in the polycondensation.
  • EP-195 604 (3) discloses polyesters for use in toner mixtures, which are obtainable by copoly-condensation of a diol component of ethoxylated or propoxylated bisphenol A with a copolymer of styrene or a styrene derivative and a carboxyl-containing vinyl monomer. These polyesters, too, do not solve the prior art problems described.
  • Toner resins which have a very high viscosity after melting or which melt only very slowly exhibit the phenomenon of cold offset, ie. toner particles are not correctly fixed on the paper and may therefore remain adhering to the fixing rollers.
  • the literature frequently describes the use of resins having a bimodal molecular weight distribution, which avoid cold and hot offset. This can also be achieved by using resin mixtures or resins having a broad molecular weight distribution.
  • the low molecular weight fraction ensures good melting of the binder and good fixing on the paper, and the higher molecular weight fraction ensures a sufficiently high viscosity of the binder and imparts to the molten toner a certain cohesion which prevents hot offset.
  • the electrostatic chargeability of toner resins is also important.
  • the charge build-up can be controlled by means of charge stabilizers.
  • Another important criterion is the stability of the charge. Many toners have a tendency of building up too much charge during the development process.
  • the charge stabilizer keeps the charge at a very particular level, and very uniform blackness of the copies is thus obtained.
  • the reaction between charge stabilizer and toner resin is the critical parameter.
  • polyester resins based on hydroxyl-containing prepolymers of olefinically unsaturated monomers which are obtainable by
  • R 1 , R 2 and R 3 are each hydrogen, methyl or ethyl and n is 1 or 2, or of a C 2 -C 10 -olefin having one or two conjugated double bonds, or of a mixture thereof,
  • R 1 is preferably hydrogen or methyl
  • suitable monomers (a) for the polymerization (1) are straight-chain or branched C 2 -C 10 -olefins, such as ethylene, propylene, 1-butylene, 2-butylene, butadiene, isoprene, 1-pentene, 2-pentene, 3-pentene, 1-hexene, 2-hexene, 3-hexene, 2,4-hexadiene, heptenes, octenes, nonenes and decenes.
  • C 2 -C 10 -olefins such as ethylene, propylene, 1-butylene, 2-butylene, butadiene, isoprene, 1-pentene, 2-pentene, 3-pentene, 1-hexene, 2-hexene, 3-hexene, 2,4-hexadiene, heptenes, octenes, nonenes and decenes.
  • Preferred monomers (a) for the polymerization (1) are styrene, ⁇ -methylstyrene, ethylene, propylene, butadiene or a mixture thereof.
  • the C 1 -C 12 -alkyl acrylates and methacrylates which are suitable as monomers (b) for the polymerization (1) carry as a straight-chain or branched alcohol radical, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, sec-amyl, tert-amyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl or n-dodecyl.
  • a straight-chain or branched alcohol radical for example methyl, ethyl, n-propyl, isopropyl, n-butyl
  • C 1 -C 4 -Alkyl acrylate and methacrylate are preferred among these.
  • Suitable C 1 -C 4 -alkyl groups which may occur as substitutents on the amide nitrogen of acrylamide or methacrylamide and on the imide nitrogen of maleimide are the abovementioned groups.
  • C 1 -C 4 -alkyl esters of acrylic and methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide and methacrylamide, or a mixture thereof, are preferred as monomers (b) for the polymerization (1).
  • the methacrylic acid derivatives give outstanding results.
  • Particularly suitable hydroxyl-containing acrylic or methacrylic acid derivatives (c) for the polymerization (1) are hydroxy-C 2 -C 4 -alkyl acrylates or methacrylates, eg. 2 -hydroxyethyl acrylate, 2 -hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 2- or 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate, N-(hydroxy-C 2 -C 4 -alkyl) -acryl-amides or -methacrylamides, eg.
  • N-(hydroxy-C 2 -C 4 -alkyl)-maleimides eg. N-(2-hydroxyethyl)-maleimide
  • hydroxyl-containing styrene derivatives eg. ortho-, meta- or para-hydroxystyrene or ortho-, meta- or para- (hydroxy-methyl)-styrene or alkenols, eg. but-2-en-1-ol or prop-2-en-1-ol (allyl alcohol)
  • alkenols eg. but-2-en-1-ol or prop-2-en-1-ol (allyl alcohol
  • Particularly suitable polyolefinically unsaturated monomers (d) are those having from 2 to 5 vinyl or allyl groups in the molecule, for example glycol di(meth)acrylate, butanediol di(meth)acrylate, glyceryl tri(meth)acrylate, (meth)allyl (meth)acrylate, penta-erythrityl triallyl ether, pentallylsucrose, di(meth)-acrylates of polyethylene glycols having a molecular weight of up to 3,000, divinyldioxane and especially divinylbenzene. If desired, the properties of the prepolymers A can be modified within certain limits by these monomers acting as crosslinking agents.
  • a hydroxyl-containing regulator is used in the polymerization (1) in order to incorporate the necessary hydroxyl groups into the prepolymer A.
  • These regulators are used in the conventional amounts, eg. from about 0.1 to 5, in particular from 0.3 to 2, % by weight, based on the total amount of the monomers (a) and (b).
  • hydroxyl-containing regulators are hydroxyl-containing mercaptans, eg. 2-hydroxy-ethyl mercaptan (2-mercaptoethanol), 1-mercapto-2,3-propanediol, 3-mercaptopropanol, 4-mercaptobutanol, 2-hydroxyethyl mercaptoacetate or 2-hydroxyethyl 3-mercaptopropionate.
  • 2-mercaptoethanol 2-hydroxyethyl mercaptan
  • a mixture of from 65 to 85% by weight of monomers (a), from 0 to 35% by weight of monomers (b), from 0 to 15% by weight of monomers (c) and from 0 to 0.5% by weight of monomers (d) are used in the polymerization (1).
  • the prepolymer A can be prepared by suspension, solution or block polymerization according to the conventional methods.
  • prepolymers A prepared by solution polymerization are preferably used since the polymerization (1) and the polycondensation (2) can then be carried out in succession in one reaction vessel because isolation of a prepolymer is dispensed with.
  • a mixture of water and a water-miscible organic solvent eg. a water/ethanol mixture or water/isopropanol mixture having a low alcohol content, or in particular water alone, is advantageously used as the suspending medium.
  • a water-miscible organic solvent eg. a water/ethanol mixture or water/isopropanol mixture having a low alcohol content, or in particular water alone.
  • polyvinylpyrrolidone is used as a protective colloid.
  • solvents are inert organic solvents, in particular aliphatic or aromatic hydrocarbons, eg. toluene, xylene, cyclohexane, methylcyclohexane, petroleum ether or naphtha.
  • aliphatic or aromatic hydrocarbons eg. toluene, xylene, cyclohexane, methylcyclohexane, petroleum ether or naphtha.
  • halohydrocarbons eg. chloroform
  • the polymerization (1) is advantageously carried out as a free radical polymerization, suitable free radical initiators being, for example, benzoyl peroxide or tert-butyl peroctanoate.
  • suitable polymerization temperature is from 60° to 130° C., in particular from 80° to 120° C. In solution polymerization, it is advantageous to use evaporative cooling.
  • the average molecular weight M n of the prepolymer A should be from 800 to 40,000, in particular from 800 to 15,000.
  • the OH number of A should be less than 60, in particular less than 50, mg of KOH/g.
  • Solution polymers A having OH numbers of from 1 to 16 mg of KOH/g and a ratio of components A to B of more than 40:60 are preferred in the polycondensation (2). If the ratio of A to B in the polycondensation (2) is less than 40:60, polymers A having OH numbers greater than 10 mg of KOH/g may also advantageously be used.
  • Particularly suitable components B for the polycondensation (2) are C 2 -C 6 -alkanediols, eg. ethylene glycol, 1,2- and 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol, ethoxylated or propoxylated bisphenol A, for example bisphenol A reacted with from 2 to 20 mol of ethylene oxide or propylene oxide, or mixtures thereof.
  • C 2 -C 6 -alkanediols eg. ethylene glycol, 1,2- and 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol, ethoxylated or propoxylated bisphenol A, for example bisphenol A reacted with from 2 to 20 mol of ethylene oxide or propylene oxide, or mixtures thereof.
  • high molecular weight polyols having an average molecular weight M n of more than 500 for example polyesterdiols, polyetherdiols or polycarbonatediols, polyesters, such as polycaprolactone or polyamides, such as polycaprolactam, may also be used.
  • dicarboxylic acids C for the polycondensation (2) are phthalic acid, isophthalic acid, terephthalic acid or their C 1 -C 4 -monoalkyl esters and in particular C 1 -C 4 -dialkyl esters or a mixture thereof.
  • cyclohexanedicarboxylic acids or aliphatic dicarboxylic acids such as succinic acid or adipic acid or the corresponding C 1 -C 4 -monoalkyl esters and in particular C 1 -C 4 -dialkyl esters may also be used.
  • a mixture of from 5 to 95% by weight of the prepolymer A, from 0 to 95% by weight of the component B and from 5 to 70% by weight of the dicarboxylic acid C or an ester thereof are used in the polycondensation (2), A and B together accounting for from 30 to 95% by weight of this mixture.
  • a mixture of from 30 to 70% by weight of A, from 10 to 50% by weight of B and from 10 to 50% by weight of C is used, A and B together accounting for from 50 to 90% by weight of this mixture.
  • tri-mellitic acid, benzoic acid, o- or p-hydroxybenzoic acid, nicotinic acid or stearic acid or the corresponding C 1 -C 4 -alkyl esters may be present as additional carboxylic acids, as well as waxes, for example polypropylene wax. These additional carboxylic acids or their esters are then present in amounts of up to 15% by weight, and the waxes in amounts of up to 15% by weight, based in each case on the total amount of the mixture of A, B and C.
  • Suitable C 1 -C 4 -alkanols in the carboxylic acid esters employed are n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol and in particular methanol and ethanol.
  • the water formed in the polycondensation (2) or the C 1 -C 4 -alkanol formed is advantageously distilled off directly from the resin melt if no entraining agent is present, or is removed by means of an entraining agent, such as toluene, xylene, methylcyclohexane or chloroform.
  • the polycondensation is usually carried out in the presence of a catalyst, for example dibutyltin oxide, a titanium alcoholate, p-toluenesulfonic acid or sulfuric acid, in the conventional amounts.
  • the polycondensation (2) is carried out either so that the prepolymer A is added to the components B and C which have been precondensed to an OH number of less than 90 mg of KOH/g, or all three components A, B and C are added together simultaneously.
  • the condensation is completed towards the end of the reaction at from 180° to 280° C.
  • the present invention furthermore relates to a process for the preparation of polyester resins based on hydroxyl-containing prepolymers of olefinically unsaturated monomers, wherein
  • R 1 , R 2 and R 3 are each hydrogen, methyl or ethyl and n is 1 or 2, or of a C 2 -C 10 -olefin having one or two conjugated double bonds, or of a mixture thereof,
  • novel polyester resins are very useful as binders for electrophotographic toners.
  • the present invention also relates to electrophotographic toners which contain, as binders, one or more novel polyester resins in the conventional amounts.
  • Electrophotographic toners are prepared from the novel polyester resins, for example, by milling the resin to a particle size of less than 1 mm, mixing it with carbon black, a magnetic pigment or a colorant, wax, if necessary a cobinder, such as a copolymer of styrene and an acrylic acid derivative or of styrene and butadiene or a polyester resin, Aerosil and a charge stabilizer, kneading this mixture to a uniform mass and then milling the latter to a particle size of from 5 to 15 ⁇ m and coating it with Aerosil in a fluid mixer.
  • a cobinder such as a copolymer of styrene and an acrylic acid derivative or of styrene and butadiene or a polyester resin
  • Aerosil and a charge stabilizer Aerosil and a charge stabilizer
  • the term pseudotoners is also used.
  • novel polyester resins are mixtures of various species of macromolecules having different average molecular weights. Since it is desirable to have toner resins with a very broad molecular weight distribution, the presence of such a mixture is partly responsible for the advantageous behavior of the novel polyester resins. Rheological tests show them to have a structurally viscous behavior.
  • novel polyester resins can be prepared reproducibly and without problems; in particular, the danger of uncontrollable crosslinking in the reaction vessel is substantially ruled out. They have good dispersing properties for carbon black, colorants, ferrites or other finely divided magnetic materials, Aerosil, charge stabilizers and waxes. They are readily millable in a reverse-jet mill and their throughput here is higher than in the case of comparable prior art resins and their content of fine dust is very low.
  • novel polyester resins have a substantially lower electrostatic chargeability compared with the prior art media, for example the resins (1). This property considerably facilitates charge stabilization of the toners which can be prepared using the novel polyester resins.
  • Toners obtained from the novel polyester resins have a long shelf life, are insensitive to moisture and exhibit good cold and hot offset properties in conjunction with a high fixing rate. Copies produced using a toner obtained from this resin have uniform blackness in the solid area and no background in unprinted areas and are fast to migration. Migration in this context means the detachment of toner particles from the copy by films, for example transparent folders.
  • a solution of 480 g of the monomer mixture, 19.2 g of benzoyl peroxide (75% strength in H 2 O) and 48 g of toluene was added dropwise to 120 g of monomer mixture (of. Table 3), 4.8 g of benzoyl peroxide (75% strength in H 2 O) and 12 g of toluene while stirring at 90° C. in the course of 2 hours, stirring was continued for 1 hour at from 90° to 100° C. and a solution of 6.0 g of benzoyl peroxide (75% strength in H 2 O) in 140 g of toluene was added dropwise while stirring in the course of 1 hour. After 5 hours at 100° C. an about 65% strength solution of the polymer in toluene was obtained.
  • a solution of 240 g of the monomer mixture, 9.6 g of benzoyl peroxide (75% strength in H 2 O) and 48 g of toluene was added dropwise to 60 g of monomer mixture (cf. Table 4), 2.4 g of benzoyl peroxide (75% strength in H 2 O) and 12 g of toluene while stirring at 90° C. in the course of 2 hours, stirring was continued for 1 hour at from 90° to 100° C. and a solution of 3.0 g of benzoyl peroxide (75% strength in H 2 O) in 70 ml of toluene was added dropwise while stirring in the course of 1 hour. After 5 hours at 100° C., an about 65% strength solution of the polymer in toluene was obtained.
  • Examples 29 to 32 were carried out similarly to Examples 19 to 22 by omitting the solvent.
  • a polyester having a glass transition temperature TG of 62° C. and a softening point SP of 135° C. was prepared similarly to Examples 40 to 52 from 305.1 g of a bisphenol A ethoxylated doubly and symmetrically, 194.2 g of dimethyhl terephthalate, 1.5 g of titanium butoxylate and 714 g of the prepolymer A from Example 23 (70% strength solution in toluene).
  • a polyester resin was prepared according to (1) from a doubly and symmetrically ethoxylated hisphenol A, a doubly and symmetrically propoxylated bisphenol A, terephthalic acid and trimellitic anhydride as the main components.
  • the resin thus prepared had an acid number of 19 mg of KOH/g, a glass transition temperature TG of 68° C. and a softening point of 148° C.
  • each polyester resin prepared according to Examples 61, 65 and 66, were headed in a Jahnke & Kunkel laboratory kneader, initially at 150° C. 5 g of carbon black (Mogul®L from Cabot) were added and kneading was then carried out for 3 hours, the temperature gradually being reduced to 90° C. Every 0.5 hour, small samples were taken from the kneader and their fine distribution was visually assessed under an optical microscope at about 700 times magnification. After 3 hours, particle size distribution in the resin was very good ( ⁇ 1 ⁇ m) to acceptable.
  • the pseudotoners were each brought to a particle size of from 5 to 15 ⁇ m by milling in a reverse-jet mill from Alpine, Type AFG (6 bar nitrogen, speed of classifier wheel 8000 rpm).
  • a strip of copy paper about 40 cm long was dusted with each of the toner powders of Experiments 76 to 78 along the length, covered with an untreated paper strip and uniformly loaded with 1.5 kg for about 5 seconds on a Kofler bench (from 50° to 270° C.).
  • the pseudotoner B described above was tested similarly.
  • the temperature for fixing on paper was determined by rubbing with the finger, Tesafilm® and an eraser.
  • the temperature at the beginning of fixing and the temperature for complete fixing were determined.
  • the pseudotoner of Examples 76 to 78 showed good fixing behavior which was similar to that of the pseudotoner of Comparative Experiment B.
  • the performance characteristics of the pseudotoners are summarized in Table 11.
  • the electrostatic chargeability of the pseudotoners of Examples 50 to 52 is substantially lower than that of comparative toner B.
  • 133 g of a polyester resin prepared according to Example 70 were headed in a Jahnke & Kunkel laboratory header at 100° C. 7 g of carbon black (Mogul L from Cabot) were added and heading was then continued for 30 hours, the temperature gradually being reduced to 70° C. Small samples were taken from the header every 0.5 h and their fine distribution was assessed visually under the optical microscope at a magnification of about 700 times. The particle size distribution in the resin was very good after 3 hours.
  • the pseudotoner was prepared by milling in a Jahnke & Kunkel laboratory mill and subsequent sieving through a 36 ⁇ m sieve to a particle size of ⁇ 36.
  • Example 79 Pigment Red 81:1 was also incorporated similarly to Examples 76 to 78. For this pseudotoner, too, no tests were carried out on the electrostatic chargeability.
  • Example 79 and Comparative Example C were also tested similarly to the fixing test on the pseudotoners, described in Examples 76 to 78.
  • the pseudotoner of Example 79 exhibited substantially lower electrostatic charging than Comparative Example C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
US08/307,790 1992-04-03 1993-03-23 Polyesters based on hydroxyl-containing prepolymers of olefinically unsaturated monomers and their use as binders for electrophotographic toners Expired - Fee Related US5494964A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4211062A DE4211062A1 (de) 1992-04-03 1992-04-03 Polyester auf Basis von hydroxylgruppenhaltigen Präpolymeren aus olefinisch ungesättigten Monomeren und ihre Verwendung als Bindemittel für elektrophotographische Toner
DE4211062.9 1992-04-03
PCT/EP1993/000696 WO1993020129A1 (de) 1992-04-03 1993-03-23 Polyester auf basis von hydroxylgruppenhaltigen präpolymeren und ihre verwendung als bindemittel

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US (1) US5494964A (de)
EP (1) EP0633906B1 (de)
JP (1) JPH07505419A (de)
KR (1) KR950700955A (de)
CA (1) CA2131097A1 (de)
DE (2) DE4211062A1 (de)
ES (1) ES2091599T3 (de)
WO (1) WO1993020129A1 (de)

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US6133354A (en) * 1998-11-17 2000-10-17 Bridgestone Corporation Copolymers as additives in thermoplastic elastomer gels
US6184292B1 (en) 1998-10-05 2001-02-06 Bridgestone Corporation Soft gel polymers for high temperature use
US6191217B1 (en) 1998-11-17 2001-02-20 Bridgestone Corporation Gels derived from polypropylene grafted alkyl vinylether-maleimide copolymers
US6204354B1 (en) 1998-05-06 2001-03-20 Bridgestone Corporation Soft compounds derived from polypropylene grafted disubstituted ethylene- maleimide copolymers
US6207763B1 (en) 1998-06-12 2001-03-27 Bridgestone Corporation Application of disubstituted ethylene-maleimide copolymers in rubber compounds
US6248825B1 (en) 1998-05-06 2001-06-19 Bridgestone Corporation Gels derived from extending grafted centipede polymers and polypropylene
US6248827B1 (en) 1997-12-22 2001-06-19 Bridgestone Corporation Centipede polymers and preparation and application in rubber compositions
US6350800B1 (en) 2000-06-05 2002-02-26 Bridgestone Corporation Soft polymer gel
US6353054B1 (en) 2000-07-31 2002-03-05 Bridgestone Corporation Alkenyl-co-maleimide/diene rubber copolymers and applications
US6359064B1 (en) 2000-09-08 2002-03-19 Bridgestone Corporation Compound of polyester and polyalkylene grafted comb polymer
US6384134B1 (en) 2000-06-05 2002-05-07 Bridgestone Corporation Poly(alkenyl-co-maleimide) and maleated polyalkylene grafted with grafting agent, and epoxy polymer
US6417259B1 (en) 2000-06-05 2002-07-09 Bridgestone Corporation Polyalkylene grafted centipede polymers
US6476117B1 (en) 2000-06-05 2002-11-05 Bridgestone Corporation Grafted near-gelation polymers having high damping properties
CN101029122B (zh) * 2006-03-03 2010-05-12 同济大学 一种丙烯酸酯改性聚酯树脂的制备方法及其用途
US20110028653A1 (en) * 2007-12-28 2011-02-03 Bridgestone Corporation Interpolymers containing isobutylene and diene mer units

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* Cited by examiner, † Cited by third party
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DE19741720A1 (de) * 1997-09-22 1999-03-25 Basf Ag Verfahren zur Herstellung einer vernetzten Polymerzusammensetzung mit Farbmitteln für elektrophotographische Toner
WO2022131220A1 (ja) * 2020-12-15 2022-06-23 東洋紡株式会社 ポリエステル樹脂
WO2023032920A1 (ja) * 2021-08-31 2023-03-09 東洋紡株式会社 ポリエステル樹脂
WO2024257553A1 (ja) * 2023-06-13 2024-12-19 東洋紡エムシー株式会社 結晶性ポリエステル樹脂水分散体、塗料組成物、塗膜及び金属缶
CN120752282A (zh) * 2023-06-13 2025-10-03 东洋纺艾睦希株式会社 结晶性聚酯树脂水分散体、涂料组合物、涂膜及金属罐

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0195604A2 (de) * 1985-03-14 1986-09-24 Kao Corporation Herstellung von Polyester und Toner, der diesen enthält
US4657837A (en) * 1980-08-15 1987-04-14 Konishiroku Photo Industry Co., Ltd. Toner for developing an electrostatically charged image
US4980448A (en) * 1988-03-17 1990-12-25 Mitsubishi Rayon Company, Ltd. Crosslinked polyester for toner and process for preparation thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4657837A (en) * 1980-08-15 1987-04-14 Konishiroku Photo Industry Co., Ltd. Toner for developing an electrostatically charged image
EP0195604A2 (de) * 1985-03-14 1986-09-24 Kao Corporation Herstellung von Polyester und Toner, der diesen enthält
US4980448A (en) * 1988-03-17 1990-12-25 Mitsubishi Rayon Company, Ltd. Crosslinked polyester for toner and process for preparation thereof

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US6248827B1 (en) 1997-12-22 2001-06-19 Bridgestone Corporation Centipede polymers and preparation and application in rubber compositions
US6599988B2 (en) 1997-12-22 2003-07-29 Bridgestone Corporation Centipede polymers and preparation and application in rubber compositions
US6248825B1 (en) 1998-05-06 2001-06-19 Bridgestone Corporation Gels derived from extending grafted centipede polymers and polypropylene
US6204354B1 (en) 1998-05-06 2001-03-20 Bridgestone Corporation Soft compounds derived from polypropylene grafted disubstituted ethylene- maleimide copolymers
US6455626B2 (en) 1998-05-06 2002-09-24 Bridgestone Corporation Gels derived from extending grafted centipede polymers and polypropylene
US6369166B1 (en) 1998-06-12 2002-04-09 Bridgestone Corporation Application of disubstituted ethylene-maleimide copolymers in rubber compounds
US6207763B1 (en) 1998-06-12 2001-03-27 Bridgestone Corporation Application of disubstituted ethylene-maleimide copolymers in rubber compounds
US6184292B1 (en) 1998-10-05 2001-02-06 Bridgestone Corporation Soft gel polymers for high temperature use
US6133354A (en) * 1998-11-17 2000-10-17 Bridgestone Corporation Copolymers as additives in thermoplastic elastomer gels
US6191217B1 (en) 1998-11-17 2001-02-20 Bridgestone Corporation Gels derived from polypropylene grafted alkyl vinylether-maleimide copolymers
US6350800B1 (en) 2000-06-05 2002-02-26 Bridgestone Corporation Soft polymer gel
US6384134B1 (en) 2000-06-05 2002-05-07 Bridgestone Corporation Poly(alkenyl-co-maleimide) and maleated polyalkylene grafted with grafting agent, and epoxy polymer
US6417259B1 (en) 2000-06-05 2002-07-09 Bridgestone Corporation Polyalkylene grafted centipede polymers
US6476117B1 (en) 2000-06-05 2002-11-05 Bridgestone Corporation Grafted near-gelation polymers having high damping properties
US6353054B1 (en) 2000-07-31 2002-03-05 Bridgestone Corporation Alkenyl-co-maleimide/diene rubber copolymers and applications
US6359064B1 (en) 2000-09-08 2002-03-19 Bridgestone Corporation Compound of polyester and polyalkylene grafted comb polymer
CN101029122B (zh) * 2006-03-03 2010-05-12 同济大学 一种丙烯酸酯改性聚酯树脂的制备方法及其用途
US20110028653A1 (en) * 2007-12-28 2011-02-03 Bridgestone Corporation Interpolymers containing isobutylene and diene mer units
US8513361B2 (en) 2007-12-28 2013-08-20 Bridgestone Corporation Interpolymers containing isobutylene and diene mer units
US9428619B2 (en) 2007-12-28 2016-08-30 Bridgestone Corporation Interpolymers containing isobutylene and diene mer units

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DE4211062A1 (de) 1993-10-07
JPH07505419A (ja) 1995-06-15
EP0633906B1 (de) 1996-09-25
DE59303983D1 (de) 1996-10-31
ES2091599T3 (es) 1996-11-01
CA2131097A1 (en) 1993-10-04
EP0633906A1 (de) 1995-01-18
WO1993020129A1 (de) 1993-10-14
KR950700955A (ko) 1995-02-20

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